期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 51, 页码 16787-16793出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b10913
关键词
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资金
- from the Japan Science and Technology Agency (JST) Core Research for Evolutional Science and Technology (CREST)
- ACCEL from the Japan Science and Technology Agency (JST) [20350030, 23245012, 25810039]
- Japan Society for the Promotion of Science (JSPS) [25-1768]
- Grants-in-Aid for Scientific Research [23245012, 20350030, 15H05479, 25810039, 26248019] Funding Source: KAKEN
Fabrication of thin films made of metal organic frameworks (MOFs) has been intensively pursued for practical applications that use the structural response of MOFs. However, to date, only physisorption-induced structural response has been studied in these films. Chemisorption can be expected to provide a remarkable structural response because of the formation of bonds between guest molecules and reactive metal sites in host MOFs. Here, we report that chemisorption-induced two-way structural transformation in a nanometer-sized MOF thin film. We prepared a two-dimensional layered-type MOF Fe[Pt(CN)(4)] thin film using a step-by-step approach. Although the as-synthesized film showed poor crystallinity, the dehydrated form of this thin film had a highly oriented crystalline nature (Film-D) as confirmed by synchrotron X-ray diffraction (XRD). Surprisingly, under water and pyridine vapors, Film-D showed chemisorption-induced dynamic structural transformations to Fe(L)(2)[Pt(CN)(4)] thin films [L = H2O (Film-H), pyridine (Film-P)], where water and pyridine coordinated to the open Fe2+ site. Dynamic structural transformations were also confirmed by in situ XRD, sorption measurement, and infrared reflection absorption spectroscopy. This is the first report of chemisorption-induced dynamic structural response in a MOF thin film, and it provides useful insights, which would lead to future practical applications of MOFs utilizing chemisorption-induced structural responses.
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